Effects of nematic coupling on the phase behaviour of nematogen mixtures

The phase behaviour of binary nematogen mixtures of side‐chain liquid crystal crosslinked polymers and low molecular weight liquid crystals is investigated with particular emphasis on the effects of nematic coupling. The cross nematic quadrupole parameter ν₁₂ is assumed to be proportional to the geometric average of ν₁₁ and ν₂₂ characteristic of single nematogens. In the weak coupling limit, the proportionality constant is lower than 1, and the phase diagram exhibits a reduced miscibility of the nematogens. In the case of strong coupling, the proportionality constant exceeds 1 resulting in higher miscibility. This is characterized by a nematic order that extends to temperatures above the upper nematic–isotropic transition temperature. A wide region of miscibility emerges showing a single nematic phase. Nematogens having similar nematic–isotropic transition temperatures exhibit different phase properties from systems with widely separated transition temperatures. Effects of the polymer volume fraction at crosslinking, rubber elasticity parameters of the network, and the Flory–Huggins interaction parameter on the equilibrium phase diagram of these systems are discussed. © 2001 Society of Chemical Industry     

Study of the effects of structural uncertainties on a fractional system of the first kind – application in vibration isolation with the CRONE suspension

In this paper, we deal with the effects of the uncertainties on a fractional system of the first kind, mainly on the frequency-domain and the time-domain responses. For the structural uncertainties, two main aspects are studied: the nonlinearities of the physical components used to realize the fractional system and the consideration of the previously neglected dynamics of the system. Both uncertainties are introduced for the hydropneumatic CRONE suspension, previously synthesized and realized without taking into consideration these uncertainties. So, the novel approach treated in this work is to find whether the uncertainties, which were previously neglected in the synthesis and the realization phases, alter the behaviour of the system or not. The results show that the fractional order system behaviour is not affected.     

Immobilised yeast grape must deacidification in a recycle fixed bed reactor

Maloalcoholic fermentation (MAF) of grape must by Schizosaccharomyces pombe immobilised in calcium‐alginate double‐layer beads (ProMalic^®) was studied in Erlenmeyer flasks and in a total recycle fixed‐bed reactor operating in batch mode. The reaction is pseudo‐first order with respect to l ‐malic acid and under similar conditions deacidification is faster in the recycle reactor. This was attributed to mass transfer limitations which were confirmed in the recycle reactor by studying the influence of yeast load on the rate of MAF. Mass transfer limitations are also responsible for the lower activation energy of fermentation with the immobilised yeast (67 ± 9 kJ mol^?1) in comparison with the free cells (126 ± 19 kJ mol^?1). Alcoholic fermentation and MAF were performed simultaneously, both in the recycle reactor and in the industrial trials, confirming the efficacy of immobilised S. pombe to reduce grape must acidity without interfering with the main fermentation. Altogether, the present results are useful for the scale‐up of a recycle reactor to process large volumes of grape must.     

HIx system thermodynamic model for hydrogen production by the Sulfur–Iodine cycle

The HI_x ternary system (H₂O–HI–I₂) is the latent source of hydrogen for the Sulfur–Iodine thermo-chemical cycle. After analysis of the literature data and models, a homogeneous approach with the Peng–Robinson equation of state used for both the vapor and liquid phase fugacity calculations is proposed for the first time to describe the phase equilibrium of this system. The MHV2 mixing rule is used, with UNIQUAC activity coefficient model combined with of hydrogen iodide solvation by water. This approach is theoretically consistent for HI_x separation processes operating above HI critical temperature. Model estimation is done on selected literature vapor–liquid, liquid–liquid, vapor–liquid–liquid and solid–liquid equilibrium data for the ternary system and the three binaries subsystems. Validation is done on the remaining literature data. Results agree well with the published data, but more experimental effort is needed to improve modeling of the HI_x system.     

Diffusion Coefficient Measurements Under Reduced Gravity Conditions by Means of the Shear Cell Technique. The Impact of Free Surfaces

A recent computational methodology is applied here in order to analyze the impact of free surfaces on the measurement of the interdiffusion coefficients if shear cells are used. Calculations indicate that the above-mentioned impact depends on the intensity of the solutal Marangoni convection but mainly on the number of active Marangoni segments, that is to say, on the extent of the free surface considered. Bulk solutal convection due to reduced gravity levels is not relevant if the gravity vector acts orthogonally to the gradient of concentration.     

Environmental aspects of ethanol-based fuels from Brassica carinata: A case study of second generation ethanol

One of the main challenges faced by mankind in the 21st century is to meet the increasing demand for energy requirements by means of a more sustainable energy supply. In countries that are net fossil fuel importers, expectation about the benefit of using alternative fuels on reducing oil imports is the primary driving force behind efforts to promote its production and use. Spain is scarce in domestic energy sources and more than 50% of the energy used is fossil fuel based. The promotion of renewable energies use is one of the principal vectors in the Spanish energy policy. Selected herbaceous crops such as Brassica carinata are currently under study as potential energy sources. Its biomass can be considered as potential feedstock to ethanol conversion by an enzymatic process due to the characteristics of its composition, rich in cellulose and hemicellulose. This paper aims to analyse the environmental performance of two ethanol-based fuel applications (E10 and E85) in a passenger car (E10 fuel: a mixture of 10% ethanol and 90% gasoline by volume; E85 fuel: a mixture of 85% ethanol and 15% gasoline by volume) as well as their comparison with conventional gasoline as transport fuel. Two types of functional units are applied in this study: ethanol production oriented and travelling distance oriented functional units in order to reflect the availability or not of ethanol supply. E85 seems to be the best alternative when ethanol production based functional unit is considered in terms of greenhouse gas (GHG) emissions and E10 in terms of non-renewable energy resources use. Nevertheless, E85 offers the best environmental performance when travelling distance oriented functional unit is assumed in both impacts. In both functional unit perspectives, the use of ethanol-based fuels reduces the global warming and fossil fuels consumption. However, the contributions to other impact indicators (e.g. acidification, eutrophication and photochemical oxidants formation) were lower for conventional gasoline.Life Cycle Assessment (LCA) procedure helps to identify the key areas in the B. carinata ethanol production life cycle where the researchers and technicians need to work to improve the environmental performance. Technological development could help in lowering both the environmental impact and the prices of the ethanol fuels.     

Bunsen section thermodynamic model for hydrogen production by the sulfur–iodine cycle

A model for the Bunsen section of the Sulfur–Iodine thermo-chemical cycle is proposed, where sulfur dioxide reacts with excess water and iodine to produce two demixing liquid aqueous phases (H₂SO₄ rich and HI rich) in equilibrium. Considering the mild temperature and pressure conditions, the UNIQUAC activity coefficient model combined with Engels' solvation model is used. The complete model is discussed, with HI solvation by water and by iodine as well as H₂SO₄ solvation by water, leading to a very high complexity with almost hundred parameters to be estimated from experimental data. Taking into account the water excess, a successful reduced model with only 15 parameters is proposed after defining new apparent species. Acids total dissociation and total H⁺ solvation by water are the main assumptions. Results show a good agreement with published experimental data between 25 °C and 120 °C.     

“Tropicalisation” of Feed-in Tariffs: A custom-made support scheme for hybrid PV/diesel systems in isolated regions

The interest and actions towards introducing renewables for off-grid regions has increased due to their ostensible cost-effectiveness, eco-friendliness and quality services provided. Nevertheless, in many isolated areas diesel generators appear as a common option, confirming that there is a need for financial support mechanisms that aid the introduction of renewables due to their higher initial investment costs.This paper proposes a so-called ‘tropicalisation’ of the Feed-in Tariff scheme to promote the introduction of hybrid systems in isolated communities based on the idea of awarding for each kWh produced by renewable energies a premium value during a guaranteed period of time. The proposed Renewable Energy Premium Tariff (RPT) scheme is an alternative mechanism to the usual initial investment donation for off-grid energy development projects by recognising the production of renewable electricity and opting for a long-term sustainability of the projects. Ecuador presents ideal conditions to study the introduction of such a ‘tropicalised’ scheme since a Feed-in Law including off-grid projects was established in 2002 and since there are governmental and local efforts for the introduction of renewable hybrids in isolated regions.Modelling of the introduction of photovoltaics (PVs) into diesel systems for several mini-grids located in isolated regions of Ecuador has been performed, and included a detailed financial analysis for optimisation of RPT values and a comparison with existing stand-alone diesel systems. The results show the cost-effectiveness of PV/diesel hybrids over diesel gensets, taking into account present and future diesel prices. To obtain long-term sustainability of the project, the RPT values are set at 0.70–1.20$ kWh covering the operability of the whole system for 20 years, where the renewable fraction should have the largest share in the hybrid system. The proposed mechanism is expected to aid the introduction of renewable technologies to bring solutions and sustainable energy options to final users of off-grid isolated regions.     

Improvement of epoxy thermosets using a thiol‐ene based polyester hyperbranched polymer as modifier

The anionic curing initiated by 1‐methyl imidazole of diglycidyl ether of bisphenol A with a hyperbranched polymer (HBP) containing long aliphatic chains in the structure were studied. The hydroxyl groups present as chain ends in the HBP structure played an important role in the curing kinetics, as demonstrated by differential scanning calorimetry, Fourier transform infrared spectroscopy and rheological studies. Properties such as shrinkage on curing and thermomechanical characteristics were also investigated. The structure of the HBP, which contains long aliphatic chains and reactive hydroxyl groups as chain ends, flexibilizes the network significantly, improving the impact resistance without notably affecting either the glass transition temperature or the microhardness of the modified thermosets. Copyright © 2012 Society of Chemical Industry